[R_S]-(-)-cholesteryl (E)-3,3-dimethyl-1-butenesulfinate | 257276-66-7

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 类固醇和类固醇衍生物
• 英文名称: [R_S]-(-)-cholesteryl (E)-3,3-dimethyl-1-butenesulfinate
• 英文别名: cholesteryl (R_S)-(E)-3,3-dimethylbutenesulfinate；(-)-cholesteryl (R)_S-(E)-t-butylethenesulfinate；[(3S,8S,9S,10R,13R,14S,17R)-10,13-dimethyl-17-[(2R)-6-methylheptan-2-yl]-2,3,4,7,8,9,11,12,14,15,16,17-dodecahydro-1H-cyclopenta[a]phenanthren-3-yl] (S,E)-3,3-dimethylbut-1-ene-1-sulfinate
• CAS: 257276-66-7
• 化学式: C₃₃H₅₆O₂S
• 分子量: 516.872
• InChiKey: ZTUWPIJCDMJEKJ-FMCBRZTFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.64
• 重原子数：
  36.0
• 可旋转键数：
  8.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.88
• 拓扑面积：
  26.3
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  环己氯化镁 、 [R_S]-(-)-cholesteryl (E)-3,3-dimethyl-1-butenesulfinate 以 苯 为溶剂， 以86%的产率得到[S_S]-(E)-3,3-dimethyl-1-butenyl cyclohexyl sulfoxide
  参考文献：
  名称：

  Andersen chemistry with an α,β-unsaturated sulfinyl chloride: synthesis and Grignard reactions of homochiral cholesteryl (R)S-(E)-t-butylethenesulfinate

  摘要：

  (-)-胆固醇基 (R)(S)-(E)-叔丁基乙烯基磺酸酯 2 通过 (E)-叔丁基乙烯基磺酰氯与 (-)-胆固醇在金鸡纳碱的存在下反应制得，以光学纯形式获得（收率约 36%）。(S)-2 的立体异构体富集版本通过提高 d.e.s 至 75% 制备。2 的 Grignard 取代反应以高度的立体专一性进行，以良好的收率和优异的 e.e. 提供了新的途径，用于获得光学 enriched 的 (E)-2-叔丁基乙烯基芳基硫醚磺酰化物。© 1999 Elsevier Science Ltd. 保留所有权利。

  DOI：

  10.1016/s0957-4166(99)00439-5
• 作为产物：
  描述：

  diphenylmethyl (E)-(3,3-dimethyl-1-butenyl) sulfoxide 在 磺酰氯 、 奎宁 作用下， 以 二氯甲烷 为溶剂， 反应 1.17h， 生成 [R_S]-(-)-cholesteryl (E)-3,3-dimethyl-1-butenesulfinate
  参考文献：
  名称：

  Synthesis and characterization of homochiral cholesteryl 1-alkenesulfinate esters

  摘要：

  A number of alpha,beta -unsaturated sulfinyl chlorides 1 has been separately prepared and treated with (-)-cholesterol under various conditions some of which incorporated chiral amines quinine or quinidine. Some (R-S) vinylic sulfinates could be isolated in enantiopure form following one or two recrystallizations of the resulting diastereomeric mixtures of (-)-cholesteryl 1-alkenesulfinates 2. Access to diastereomerically enriched (S-S) vinylic sulfinates (66-75% de) was achieved in three instances. Absolute stereochemical assignments were made with the assistance of the chiral solvating agent (R)-2,2,2-trifluoro-1-(9-anthryl)ethanol. (C) 2001 Elsevier Science Ltd, All rights reserved.

  DOI：

  10.1016/s0957-4166(00)00474-2

文献信息

• Stereospecific Grignard reactions of cholesteryl 1-alkenesulfinate esters: Application of the Andersen Protocol to the preparation of non-racemic α,β-unsaturated sulfoxides
  作者：Rick R Strickler、John M Motto、Craig C Humber、Adrian L Schwan

  DOI：10.1139/v03-002

  日期：2003.6.1

  Enantiomerically enriched α,β-unsaturated sulfinate esters of (–)-cholesterol undergo stereospecific substitutions at sulfur when treated in benzene at 6°C with Grignard reagents. Sulfoxides with ees of 85–99.5% are obtained when enantiopure sulfinates are used. The substitution reactions proceed with inversion of sulfur configuration. Enantiomerically pure cholesteryl (E)-2-carbomethoxyethenesulfinate is not a suitable reactant under the Grignard reaction conditions. It is suggested that the ester group induces unwanted reactions significantly lowering both the yield and sulfur stereogenicity.Key words: sulfinate, sulfoxide, Grignard reagents, stereospecific, unsaturated.

  旋光富集的α，β-不饱和亚磺酸酯(–)-胆固醇在苯中与格氏试剂在6°C下反应时，在硫原子上发生立体特异性取代反应。当使用对映纯的亚磺酸酯时，可以获得ee值为85-99.5%的亚砜。取代反应会导致硫原子构型的倒转。旋光纯的胆固醇(E)-2-羰基甲氧基乙烯基亚磺酸酯在格氏反应条件下不是一个合适的反应物。建议酯基诱导了不必要的反应，显著降低了产率和硫立体选择性。关键词：亚磺酸酯，亚砜，格氏试剂，立体特异性，不饱和。